EP0548522B1 - Process for the purification of 2,3-pyridine and quinolinedicarboxylic acid diester compounds - Google Patents
Process for the purification of 2,3-pyridine and quinolinedicarboxylic acid diester compounds Download PDFInfo
- Publication number
- EP0548522B1 EP0548522B1 EP92119140A EP92119140A EP0548522B1 EP 0548522 B1 EP0548522 B1 EP 0548522B1 EP 92119140 A EP92119140 A EP 92119140A EP 92119140 A EP92119140 A EP 92119140A EP 0548522 B1 EP0548522 B1 EP 0548522B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- diethyl
- solvent
- pyridinedicarboxylate
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 31
- -1 quinolinedicarboxylic acid diester compounds Chemical class 0.000 title claims abstract description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000746 purification Methods 0.000 title claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 28
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 23
- 239000011707 mineral Substances 0.000 claims abstract description 23
- 238000000605 extraction Methods 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 38
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 23
- VSPXTWXXNZJEHM-UHFFFAOYSA-N diethyl 5-ethylpyridine-2,3-dicarboxylate Chemical group CCOC(=O)C1=CC(CC)=CN=C1C(=O)OCC VSPXTWXXNZJEHM-UHFFFAOYSA-N 0.000 claims description 16
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 15
- 239000000284 extract Substances 0.000 claims description 15
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 13
- 239000011260 aqueous acid Substances 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 125000004769 (C1-C4) alkylsulfonyl group Chemical group 0.000 claims description 3
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- UUJUSJLHSWGXPA-UHFFFAOYSA-N diethyl 5-(methoxymethyl)pyridine-2,3-dicarboxylate Chemical compound CCOC(=O)C1=CC(COC)=CN=C1C(=O)OCC UUJUSJLHSWGXPA-UHFFFAOYSA-N 0.000 claims description 3
- KIDQHBXPNBCITQ-UHFFFAOYSA-N diethyl 5-methylpyridine-2,3-dicarboxylate Chemical compound CCOC(=O)C1=CC(C)=CN=C1C(=O)OCC KIDQHBXPNBCITQ-UHFFFAOYSA-N 0.000 claims description 3
- ICMBEQVDQPLOFB-UHFFFAOYSA-N diethyl quinoline-2,3-dicarboxylate Chemical compound C1=CC=C2N=C(C(=O)OCC)C(C(=O)OCC)=CC2=C1 ICMBEQVDQPLOFB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- LIVYVINPLCASPD-UHFFFAOYSA-N diethyl pyridine-2,3-dicarboxylate Chemical compound CCOC(=O)C1=CC=CN=C1C(=O)OCC LIVYVINPLCASPD-UHFFFAOYSA-N 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 2
- 229940117389 dichlorobenzene Drugs 0.000 claims 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 235000010755 mineral Nutrition 0.000 description 12
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical class OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 7
- BPPSPXOWNGOEGL-UHFFFAOYSA-N 2-(4,5-dihydro-1h-imidazol-2-yl)pyridine Chemical compound N1CCN=C1C1=CC=CC=N1 BPPSPXOWNGOEGL-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000004009 herbicide Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000002363 herbicidal effect Effects 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 150000003248 quinolines Chemical class 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006286 aqueous extract Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
Definitions
- the present invention relates to an efficient process for the purification of 2,3-pyridine and quinolinedicarboxylic acid diesters of formula I wherein X and Y are each independently hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxyalkyl, C 1 -C 6 alkoxy, C 1 -C 4 alkylthio, phenoxy, C 1 -C 4 haloalkyl, nitro, cyano, C 1 -C 4 alkylamino, diloweralkylamino, C 1 -C 4 alkylsulfonyl or phenyl optionally substituted with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen group; and, when taken together, X and Y may form a ring in which XY is represented by the structure wherein L, M, Q and Z are each hydrogen, halogen, C 1 -C
- the process of the invention avoids the use of time-consuming distillation purification procedures. Furthermore, the mineral acid present in the aqueous acid solution, after extraction with a solvent, is readily recycled into the process of the invention.
- the formula I pyridine and quinolinedicarboxylic acid diester compounds are purified by washing a mixture of an impure formula I compound and a solvent with between about 0.2 to 1.2 molar equivalents of a 5% to 20%, by weight, mineral acid solution, extracting the washed organic mixture with at least about 2.0 molar equivalents, preferably about 2.0 to 6.0 molar equivalents, of a 40% to 85%, by weight, mineral acid solution, diluting the concentration of the mineral acid in the aqueous acid extract to a value of about 5% to 30%, by weight, with water and extracting the diluted aqueous acid extract with a solvent to obtain purified formula I compounds.
- the dilute acid wash removes acid soluble impurities from the impure formula I compound. Since the acid soluble impurities are removed, a purer formula I compound is obtained from the aqueous mineral acid extraction.
- Another embodiment of the invention comprises extracting an impure formula I compound, optionally in the presence of a solvent, with at least about 2.0 molar equivalents, preferably about 2.0 to 6.0 molar equivalents, of a 40% to 85%, by weight, mineral acid solution, diluting the concentration of the mineral acid in the aqueous acid extract to a value of 5% to 30%, by weight, with water and extracting the diluted aqueous acid extract with a solvent to obtain purified formula I compounds.
- a further embodiment of the invention comprises extracting an impure formula I compound, optionally in the presence of a solvent, with at least about 2.0 molar equivalents, preferably about 2.0 to 6.0 molar equivalents, of a 40% to 85%, by weight, mineral acid solution, neutralizing the aqueous acid extract with base and extracting the neutralized aqueous extract with a solvent to obtain purified formula I compounds.
- the purified formula I compounds may be isolated by evaporating the resultant extract, or the extract containing the purified formula I compound may be sent directly to the reaction used to obtain the corresponding pyridine or quinolinedicarboxylic acid compound.
- Mineral acids which are suitable for use in the present invention include sulfuric acid, hydrochloric acid, hydrobromic acid, phosphoric acid with sulfuric acid being preferred. A 45% to 65%, by weight, mineral acid solution is preferred.
- Solvents which are useful in the present invention include aromatic hydrocarbons such as toluene, benzene and xylenes, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzenes. Toluene and chlorobenzene are preferred solvents.
- Bases suitable for use in the process of the invention include ammonium hydroxide, sodium carbonate, sodium bicarbonate with ammonium hydroxide being preferred.
- Preferred formula I compounds that are purified by the processes of the invention are diethyl 5-ethyl-2,3-pyridinedicarboxylate, diethyl 2,3-pyridinedicarboxylate, diethyl 5-methoxymethyl-2,3-pyridinedicarboxylate, diethyl 2,3-quinolinedicarboxylate and diethyl 5-methyl-2,3-pyridinedicarboxylate.
- the processes of the invention provide purified formula I compounds without requiring the use of arduous or time consuming distillations done at high temperatures and high vacuum.
- the purified formula I compounds are useful as starting materials for the preparation of herbicidal 2-(2-imidazolin-2-yl)pyridine and quinoline compounds having the structural formula II wherein
- HPLC designates high pressure liquid chromatography
- a 15%, by weight, sulfuric acid solution (0.200 mol) is added with,stirring to a solution of diethyl 5-ethyl-2,3-pyridinedicarboxylate (100.00 g, 50.3% real, 0.200 mol) in toluene (400 mL).
- the organic layer is separated and extracted with 60%, by weight, sulfuric acid solution (0.651 mol).
- the aqueous extract is diluted with ice-water (316.50 g) and extracted with toluene (200 mL).
- the organic extract (228.4 g) is concentrated in vacuo to give purified diethyl 5-ethyl-2,3-pyridinedicarboxylate (55.26 g, 77.2% real, isolated yield 84.8%).
- a solution of diethyl 5-ethyl-2,3-pyridinedicarboxylate (34.46 g, 72.6% real, 0.10 mol) in toluene (65.54 g) is extracted with a 32.36%, by weight, sulfuric acid solution (0.2 mol).
- the organic phase is washed with 10% sodium bicarbonate solution and water.
- the combined water and sodium bicarbonate washes are washed with toluene and the toluene wash is combined with the organic phase.
- the organic phase is concentrated in vacuo to a constant weight and the unextracted diethyl 5-ethyl-2,3-pyridinedicarboxylate is then assayed by HPLC.
- Table I The results of this example are summarized in Table I below.
- the purity of the diethyl 5-ethyl-2,3-pyridinedicarboxylate is generally improved to greater than 81% (up from 72.6%) using 2-6 equivalents of sulfuric acid solutions having concentrations greater than 43%.
- the increase in purity from 72.6% to generally greater than 81% may not appear to be a significant increase, it results in a dramatic improvement when commercially manufacturing the 2-(2-imidazolin-2-yl)pyridine and quinoline herbicides.
- mineral acid solutions the purity of the diethyl 5-ethyl-2,3-pyridine dicarboxylate is improved to 82% to 85%.
- Diethyl 5-ethyl-2,3-pyridinedicarboxylate (29.0 g, 70.2% real, 0.081 mol) is added to a stirred mixture of water (50 mL) and 96% sulfuric acid (30.37 g). The mixture is allowed to settle and the phases are separated. The aqueous layer, which contains a small amount of an oil, is stirred with diatomaceous earth (2.0 g), filtered and washed with water (10 mL). The combined filtrate and wash is neutralized with 30% ammonium hydroxide solution (36.22 g) and extracted with toluene. The combined organic extracts are concentrated in vacuo to obtain a brown oil and a small amount of a solid. The oil is decanted from the solid to give purified diethyl 5-ethyl-2,3-pyridinedicarboxylate (19.78 g, 81.5% real, 79.2% real recovery).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US812517 | 1991-12-20 | ||
| US07/812,517 US5276157A (en) | 1991-12-20 | 1991-12-20 | Process for the purification of 2,3-pyridine and quinolinedicarboxylic acid diester compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0548522A1 EP0548522A1 (en) | 1993-06-30 |
| EP0548522B1 true EP0548522B1 (en) | 1997-01-29 |
Family
ID=25209819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92119140A Expired - Lifetime EP0548522B1 (en) | 1991-12-20 | 1992-11-09 | Process for the purification of 2,3-pyridine and quinolinedicarboxylic acid diester compounds |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5276157A (da) |
| EP (1) | EP0548522B1 (da) |
| AT (1) | ATE148457T1 (da) |
| BR (1) | BR9205095A (da) |
| DE (1) | DE69217193T2 (da) |
| DK (1) | DK0548522T3 (da) |
| ES (1) | ES2096701T3 (da) |
| GR (1) | GR3022449T3 (da) |
| HK (1) | HK1000105A1 (da) |
| IL (1) | IL104136A (da) |
| TW (1) | TW261611B (da) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3782985A1 (en) | 2019-08-19 | 2021-02-24 | BASF Agrochemical Products B.V. | Process for manufacturing 5-methoxymethylpyridine-2,3-dicarboxylic acid derivatives |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4460776A (en) * | 1982-05-25 | 1984-07-17 | American Cyanamid Company | Process for the preparation of 6-substituted-2,3-pyridinedicarboxylic acid diesters |
| US4723011A (en) * | 1985-10-28 | 1988-02-02 | American Cyanamid Company | Preparation of substituted and disubstituted-pyridine-2,3-dicarboxylate esters |
| GB8709228D0 (en) * | 1987-04-16 | 1987-05-20 | Shell Int Research | Preparation of heterocyclic compounds |
| EP0296109A3 (de) * | 1987-06-18 | 1989-12-20 | Ciba-Geigy Ag | 2-(Imidazolin-2-yl)nicotinsäurederivate |
| JPH0625116B2 (ja) * | 1987-07-08 | 1994-04-06 | ダイソー株式会社 | ピリジン−２，３−ジカルボン酸誘導体の製造法 |
| DE68929429T2 (de) * | 1988-03-18 | 2003-06-18 | Sugai Chemical Industry Co, Ltd. | Verfahren zur Herstellung von Pyridin-2,3-Dicarbonsäure-Verbindungen |
| US4904816A (en) * | 1989-06-15 | 1990-02-27 | American Cyanamid Company | Process for the manufacture of anilinofumarate via chloromaleate or chlorofumarate or mixtures thereof |
| US5124458A (en) * | 1990-06-15 | 1992-06-23 | American Cyanamid Company | Process for the preparation of dialkyl pyridine-2,3-dicarboxylate and derivatives thereof from dialkyl dichlorosuccinate |
-
1991
- 1991-12-20 US US07/812,517 patent/US5276157A/en not_active Expired - Fee Related
-
1992
- 1992-11-09 EP EP92119140A patent/EP0548522B1/en not_active Expired - Lifetime
- 1992-11-09 ES ES92119140T patent/ES2096701T3/es not_active Expired - Lifetime
- 1992-11-09 AT AT92119140T patent/ATE148457T1/de not_active IP Right Cessation
- 1992-11-09 DK DK92119140.9T patent/DK0548522T3/da active
- 1992-11-09 DE DE69217193T patent/DE69217193T2/de not_active Expired - Fee Related
- 1992-11-13 TW TW081109093A patent/TW261611B/zh active
- 1992-12-17 IL IL10413692A patent/IL104136A/xx not_active IP Right Cessation
- 1992-12-18 BR BR9205095A patent/BR9205095A/pt not_active Application Discontinuation
-
1997
- 1997-01-31 GR GR960402833T patent/GR3022449T3/el unknown
- 1997-07-17 HK HK97101565A patent/HK1000105A1/xx not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| HK1000105A1 (en) | 1997-11-28 |
| DE69217193T2 (de) | 1997-05-15 |
| ATE148457T1 (de) | 1997-02-15 |
| GR3022449T3 (en) | 1997-04-30 |
| TW261611B (da) | 1995-11-01 |
| IL104136A0 (en) | 1993-05-13 |
| ES2096701T3 (es) | 1997-03-16 |
| DE69217193D1 (de) | 1997-03-13 |
| EP0548522A1 (en) | 1993-06-30 |
| US5276157A (en) | 1994-01-04 |
| BR9205095A (pt) | 1993-06-22 |
| DK0548522T3 (da) | 1997-02-17 |
| IL104136A (en) | 1997-02-18 |
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